DK168348B1 - Stabilised liquid herbicidal preparation which comprises phenmedipham or desmedipham, or mixtures thereof, and a process for producing such a preparation, and a use of the preparation - Google Patents

Description

DK 168348 B1

The present invention relates to a stabilized liquid herbicide composition containing phenmedipham and / or desme-dipham, which is in the form of an emulsion containing 5-40% by weight of phenmedipham and / or desmedipham dispersed in a liquid phase consisting essentially of mineral oil and / or vegetable oil, a surfactant component and optionally water, and the composition comprises 15-65% by weight of one or more mineral oils and / or vegetable oils, 5-40% by weight of a surfactant component and up to 40% water, and which composition is capable of forming a stable ready-to-use oil-in-water emulsion or micro-emulsion by mixing with water in a ratio of 1 part preparation to 1-10 parts water, and which optionally also contains metamitron, chloridazone or ethofumesate.

The invention further relates to a process for the preparation of such a composition and to a use of the composition.

British Patent No. 1,127,050 discloses substituted phenylcarbamates of the general formula A

0 1 / Ri o-c-tf HH- £ -0-R3

ISLAND

Wherein R 1 represents an alkyl group, a cycloalkyl group or an aryl group, which aryl group may be substituted by a halogen atom and / or an alkyl group and / or a trifluoromethyl group, R 2 represents a hydrogen atom or an alkyl group, or R the nitrogen atom may form a heterocyclic ring which may contain additional nitrogen and / or oxygen atoms, and R 3 represents an alkyl, alkenyl or alkynyl group which may be substituted by a terminal halogen atom which compounds may be used to selectively control of weeds in crop areas. The herbicidal effect DK 168348 B1 2 is observed both in pre-run and post-run treatments, and this allows compositions containing these for compounds A to be applied by any desired method. Herbicidal activity is also observed when Compound A is applied to the leaves of established weeds and the compounds are particularly useful for controlling weeds in beet fields, especially as post-emergence herbicides in beet fields.

A particularly preferred compound of general formula A is methyl (3- (3-tolyl-carbamoyloxy) phenyl) carbamate, which compound was later named phenmedipham. Another particularly preferred compound is ethyl (3-phenyl-carbamoyl oxyphenyl) carbamate, which was later named desme-dipham. Methyl (3- (3-tolyl-carbamoyloxy) phenyl) carbamate is commercially available under the trademark Betanal® and is used especially as a post-herbicide for weed control in beet crops, especially in sugar beet, at an added amount of 1 kg of active substance / 200-300. 1 / ha. It has been reported (Pesticide Manual. A World Compendium, The British Crop Protection Council, 6th edition, 1979) that the compound acts through the leaves 20 and has little effect through the soil and roots. In the soil, at 3 months, there was a 71-86% degradation of the active substance detected 1 day after the treatment.

Preparation of the compounds A is carried out according to the British patent in organic solvents such as 25 tetrahydrofurans or anhydrous pyridine.

Danish Patent Application No. 2210/85 relates to a process for the preparation of substituted phenylcarbamates in an aqueous medium, cf. DK 159653 B.

After the synthesis, the reaction product, which is highly soluble in water, can either be isolated and purified in the usual manner, for example, by filtration and washing with water followed by drying, or removed from the aqueous phase by extraction with an organic solvent (or an organic solvent). solution mixture which is substantially immiscible with water or only slightly miscible with water.

Normally, a drying process leads to some degradation of the final product, which is why exclusion of the drying step is advantageous.

The substituted phenylcarbamates (phenmedipham and desme-dipham) can be used either alone or in admixture with each other and / or with other herbicides and / or other substances, eg fertilizers, for the control of weeds.

They can be used in the form of concentrated preparations for dilution with water at the point of use.

It has now been found that some substituted phenyl carbamate, namely phenmedipham and desmedipham, may, together with other herbicides, be particularly advantageously formulated in oily preparations, which are described in more detail below.

In formulating commercial liquid herbicide concentrates with substituted phenylcarbamates, it is normal to incorporate a solvent capable of dissolving the phenylcarbamate and facilitating the subsequent dilution of the composition at the site where the composition is to be used. Isophorone is usually used as a solvent in formulating such preparations, since isophorone is a fairly good solvent for the phenyl carbamates and since the phenyl carbamates are chemically relatively stable in solution in isophorone, especially when the phenyl carbamates have been washed or treated with acid at a pH of approx. 2-4 before the solution in isophorone. Another advantage of using isophorone is that it is only slightly soluble in water (if a water-soluble solvent was used in the concentrate, it would tend to dissolve in the aqueous phase when the ready-to-use liquid preparation was to be prepared on site. by adding water, which would precipitate the phenylcarbamate with a decrease in biological activity and blockage of the spraying equipment ').

It is normal to incorporate ionic emulsifiers such as calcium dodecylbenzenesulfonate in commercial solutions of 5 phenmedipham in isophorone. It has also been proposed to use salts of phosphoric acid esters as emulsifiers.

As an interesting alternative to solutions of phenylcarbamates in isophorone, it has been found according to the invention that the biological activity of substituted phenylcarbamates is advantageously large when the phenylcarbamates are "activated" by being presented unresolved in the form of suspensions of the compounds in finely ground liquid phase state comprising one or more oily components and one or more surfactants, the liquid phase being capable of forming an oil-in-water emulsion or a microemulsion when mixed with water at the site of use in preparing the final ready-to-use preparation.

The present invention thus relates to a stabilized liquid herbicide composition containing phenmedipham and / or desmedipham, which is in the form of an emulsion containing phenmedipham and / or desmedipham dispersed in a liquid phase consisting mainly of mineral oil and / or vegetable oil, a surfactant and optionally water, the composition comprising 25 a) 5-40% by weight of phenmedipham and / or desmedipham having a particle size less than 10 microns, b) 15-65% by weight of one or more mineral oils and / or vegetable oils, c) 5-40% by weight of a surfactant containing 30 or more surfactants, and d) up to 40% by weight of water, which is capable of forming a stable ready-to-use oil. -water emulsion or micro-emu- sion by mixing with water in a ratio of 1 part preparation to 1-10 parts water.

Examples of mineral oils include spindle oil, aromatic compounds such as paraffinic oils, etc .; Examples of vegetable oils include soybean oil, canola oil, olive oil, etc.

The suspensions of the phenylcarbamates in oily components and surfactants have a content of oily substance 10 of approx. 15-65% by weight, based on the composition. The surfactant (s) which may be selected from the group consisting of nonionic, anionic, ampholytic and cationic surfactants and mixtures thereof will be present in an amount of 5-40% by weight based on the weight of the composition. The amount of phenmedipham and / or desmedipham may be between 5 and 40% by weight, based on the composition. In addition to the phenyl carbamates, the oily component and the surfactant, the liquid phase of these concentrated preparations may contain one or more constituents selected from the group 20 consisting of glycols, glycol ethers and combinations thereof, usually in concentrations of 0.1-15%. especially 2-10%, based on the weight of the composition. Furthermore, water may be incorporated in an amount of up to 40% by weight. In practice, consideration will be given to the chemical stability of the phenylcarbamate in the individual formulation, which will determine the maximum amount of water that can be added. If water is incorporated into the oil / detergent mixture, the pH should be adjusted to be in the acidic range, preferably in the optimal range of 2-4, to ensure optimal chemical stability of the phenylcarbamate.

The oily component and the surfactant may be selected so as to be mutually soluble to form a stable solution which can effectively suspend the finely divided phenylcarbamates and so that the surfactant will effectively emulsify the oil when water is added. 35 formation of the final ready-to-use preparation. The surfactant may also help to effectively moisten the sprayed surface with the composition. The oily component and the detergent and relative amounts thereof can also be selected to form a microemulsion when mixed with an equal amount of water or up to a 10 times as much water (a microemulsion is characterized by: include oil, emulsifier (surfactant) and finely divided water, and being clear and transparent. A microemulsion is stable and usually cannot be separated by centrifugation). The advantage of selecting the oily component and the surfactant in such a way that they form a microemulsion is, inter alia, that the phenylcarbamate can be added to the oily component / surfactant in a wet state, i.e. that it is not necessary to completely dry the phenylcarbamate produced by the process of the invention before combining it with the oily component / surfactant. Another advantage of choosing the oily component and the surfactant in such a way that they can form a microemulsion is that the microemulsion, due to its inherent stability, tends to hold the suspension of phenyl carbamate a stable during transport and handling of the preparation, thereby avoiding sedimentation problems. A further advantage associated with microemulsion form preparations is that the dilution with water to prepare ready-to-use solutions takes place without problems such as lump formation, etc.

Useful surfactants are nonionic compounds such as polyethoxylated alkyl phenols, polyethoxylated higher alkanols, polyethoxylated fatty acids, polyethoxylated amines and amides, monoglycerides and derivatives thereof. Alkylarylsulfonic acids and phosphoric acid esters and salts thereof will also be useful surfactants. Phosphoric acid esters may be mono- and diesters of polyethoxylated higher alkanols, polyethoxylated alkyl phenols, polyethoxylated distyryl and tristyryl phenols, and non-ethoxylated alcohols. Furthermore, ampholyts will be useful surfactants. Other surfactants are, for example, as described in McCutcheon's publication: Detergent & Emulsifiers, International Edition, 1983, Glen Rock, New Jersey 07452, U.S.A. Of course, similar surfactants from other sources can also be used.

It is believed to be advantageous to use mixtures of ethoxylated surfactants and anionic surfactants, preferably a non-ionic / anionic mixture, when the nonionic components constitute a mixture of surfactants with HLB values of about 10%, respectively. . 9 (emulsifier) and approx. 12-13 (wetting agent and dispersant).

In the preparation of the substituted phenylcarbamate composition, the surfactants may be mixed with the oily component to form a translucent solution. In this solution, crude ground dry substituted phenylcarbamate is slurried. The mixture can be further ground, for example, in a ball mill, whereby at least 99% of the substituted phenylcarbamate is obtained with a particle size of less than 10 microns and 50% with a particle size of less than 3-5 microns.

When the substituted phenylcarbamate prepared in aqueous solution is isolated as a wet paste, the dry matter content will normally be about 65-70% after centrifugation. It is possible to use this material suspended in the oil / detergent mixture, whereby the water is incorporated into the mixture so that the liquid phase comprises a stable microemulsion which can be further ground in the ball mill. In another embodiment, the herbicidally active compound or the herbicidally active compounds in the form of an aqueous slurry may be ground to comminute the compound or compounds to a size suitable for incorporation into the final composition, optionally with the addition of a surfactant. whereupon the liquid comprising one or more oily components and one or more surfactants is added, or the ~ 35 components which constitute this liquid are added separately. In each case, the resulting liquid phase will thereby form an emulsion or microemulsion. This is believed to be an advantageous method of utilizing the aqueous slurry prepared by the above-described aqueous phase synthesis.

Smaller amounts of glycol ethers, e.g., butyl glycol, will probably have an advantageous effect on viscosity and at the same time allow for a wider mixing ratio between the microemulsion and water when the preparation is to be diluted at the site where the preparation is to be used. Small amounts of water in the composition will often have a viscosity regulating effect, and glycols such as propylene glycol will stabilize mixtures containing limited amounts of water. The dispersion must have sufficient viscosity. On the one hand, it must be so light that the dilution of the water for dilution occurs rapidly, and on the other hand it must be sufficiently viscous to prevent sedimentation of the active substances.

Several patents and other literature describe the preparation of herbicide preparations with phenylcarbamates as active ingredient. However, they can be divided into two groups, namely (1) where the active substance is dissolved in an organic solvent and then emulsified in water by a wide variety of emulsifiers to form ready-to-use solutions, and (2) where the active substance is dispersed in water using over 25 surfactants of various kinds.

The compositions dispersed in oily liquid, with the toxin content of the same asset, have as strong an effect as solvent-based compositions and effects which are considerably greater than those dispersed in water.

30 Application amounts in the order of approx. 0.3 kg of active substance / ha has been found to be suitable for selective control of weeds when two or more applications are carried out during the growing season or when the active substance is sprayed via a spray gun. In other cases, an application rate of approx. 1 kg of active substance / ha is usually sufficient.

The above-described method for preparing oil-based compositions can be used not only for preparations containing the substituted phenylcarbamates, but also for the preparation of other preparations which also include other types of herbicides and pesticides. Examples of herbicides include 5-amino-4-chloro-2-phenyl-3 (2H) -pyridazinone (chloridazone), 2-ethoxy-2,3-dihydro-3,3-dimethylbenzofuran-5-yl-methanesulfo -10 night (ethofumesate) and 4-amino -4,5-dihydro-3-methyl-6-phenyl-1,2,4-triazin-5-one (metamitron).

Thus, compositions comprising both the phenyl carbamates and components which may be metamitron are advantageous in that the content of each active ingredient can be kept at a lower level, since the preferred phenyl carbamate is more active per liter. unit of weight than the other herbicidal active compounds mentioned above.

The above-mentioned compound metamitron is used as a herbicide for beets, usually at a dose of approx. 3-4 kg / ha. When in some cases, meta-20 mitron is preferred instead of phenylcarba mater used at doses of only approx. 1 kg / ha, this is due to the fact that metamitron has a better biological effect against cages (Galium aparine), harem food (Lapsana communis) and black night shade (Solanum nigrum). A much better biological effect is obtained by controlling yellow bovine eye (Chrysanthemum segetum), smelling chamomile (Matricaria chamomilla), little nettle (Urtica impure) and annual grasses (Poa annua). The other 15-20 weed species in beets, which are common in Denmark, are just as well controlled with phenmedipham as with metamitron.

30 It should also be added that at a dose of 3-4 kg / ha, metamitron is less aggressive (phytotoxic) to beet plants than phenmedipham used at a dose of 1 kg / ha.

DK 168348 B1 10

Farmers often prefer to use a mixture of meta-mitron and phenmedipham in which each of the preparations is used at a dose which is half the normal dose. In this way, a biological effect can be obtained which is completely 5 goals with The herbicidal mixture is also no more phytotoxic than when metamitron is used alone.

Metamitron is usually commercially available as a 70% wettable powder and phenmedipham as a 16% is emulsion 10 containing isophorone. So far, farmers have themselves mixed the preparations for the spraying. However, it is not practical for the user to mix two types of preparations which are so different. The mixture is best done by diluting each preparation separately in a portion of the dilution water and then making the mixture. To activate the metamitron biologically, mineral oil is often added which is emulsified in the syringe solution. Therefore, there will be a risk of spraying problems (nozzle stop) if the mixture is not taken carefully. When using multiple products, there will be a greater risk of misallocating the products.

Finally, using the present product, which is characterized in that both phenmedipham and metamitron are dispersed in an oil / surfactant mixture, the user - contrary to current practice - avoids a total of 25 dust from the wettable powder. and that isophorone is not used as a solvent.

Thus, an interesting aspect of the present invention is a composition comprising phenmedipham or desme-dipham in an amount of ca. About 6% by weight, metamitron in an amount of 5-40% by weight, preferably 10-30% by weight, e.g. 17% by weight, formulated with an oily component such as mineral oil, e.g., spindle oil, in an amount of approx. 30% by weight, a surfactant or surfactant mixture containing ethoxylated nonylphenol (3-9 35 ethylene oxide units per molecule) and optionally a phosphoric acid salt such as Berol ™ 724 monoethanolamine salt and / or DK or 168348 B1 an alkyl or aryl or alkylaryl sulfonic acid salt such as dodecylbenzenesulfonic acid triethanolamine salt or a linear C10-2 2'alkylsulfonic acid salt (LAS) 'wherein the total amount of surfactant or surfactant mixture is about 40% by weight, butyl glycol in an amount of 0-10% by weight, e.g. 7.5% by weight, and optionally water, all quantities being based on the total weight of the preparation. A mixed composition can be prepared by mixing a dispersion containing phenmedipham and a dispersion containing metamitron, which dispersions can be prepared individually in liquid phases comprising an oily component such as spindle oil in an amount of about 30-35%, a surfactant mixture consisting of an alkyl or aryl or alkylarylsulfonic acid salt such as dodecylbenzenesulfonic acid triethanolamine salt, ethoxylated nonylphenol and butyl glycol.

The solubility of phenmedipham and metamitron in mineral oil is approx. 0.1%, depending on the content of aromatics in the oil. In the water-emulsifiable liquids described above, which are solutions comprising oil and surfactant, the solubility of phenmedipham and metamitron is about 3% when the surfactant content of the liquid is of the same order of magnitude as the oil content. However, at such a high solubility, there may be a tendency for slow crystal growth of phenmedipham and / or metamitron in the dispersions under storage under different temperature conditions, which means that the compositions will be less stable under such conditions. In microemulsions with a content of approx. 25% water reduces the solubility of phenmedipham by a factor of 10 to approx. 0.3%. A similar reduction does not occur for 30 metamitrons. Moreover, diluting methamitrone dispersions in water tends to be more time-consuming than phenmedipham dispersions, probably due to the dissolved proportion of metamitron. However, when emulsions or microemulsions are formed by dilution, they are very stable.

DK 168348 B1 12

In order to lower the solubility of phenmedipham and metamitron in the liquid and to counteract the tendency of metamitron preparations to dilute with water more slowly, the proportion of oil in the liquid can be kept high and the proportion of surfactant 5 correspondingly low and an oil may be used which has a limited aromatic content, ie. a content of less than 30% by weight, preferably less than 10% by weight. (As an example of a preferred oil for this purpose, mention may be made of a mineral oil having a boiling point above 200 ° C and a viscosity of 10 below 100 cSt at 40 ° C and, as mentioned above, an aromatic content of less than 30% by weight, preferably at less than 10% by weight). However, it has been found that if the amount of oil is increased to approx. 60% and the amount of surfactant is reduced to approx. 10-15%, there will be a pronounced tendency for the composition to secrete sticky sediments of oil and fine-grained herbicide when diluted with water. The proportion of oil emulsified in the aqueous phase will also tend to be excreted again as an upper phase.

Thus, in preparations with a high content of low aromatic oil, there is a pronounced need to use a highly effective emulsifier (surfactant) system. A sufficiently effective emulsifier system (surfactant system) which will ensure a satisfactory emulsification of relatively low aromatic mineral oils can be obtained, for example, by replacing a portion of the above-mentioned ethoxylated nonylphenols with ethoxylated dinonylphenols and combining them with either phosphoric acid salts such as Berol ™ 724 monoethanolamine salt and / or an alkyl or aryl or alkylarylsulfonic acid ester salt such as dodecylbenzenesulfonic acid triethanolamine salt, the total amount of surfactant being about 10-15%, based on the composition, and the amount of low-aromatic mineral oil, e.g., solvent-refined paraffinic mineral oil, is approx. 60% by weight. Part of the oil can be replaced with a lower-boiling petroleum fraction such as petroleum. Thus, interesting compositions according to the invention comprise 15-40% by weight, preferably 20-30% by weight, of either phenmedipham or a combination of phenmedipham and metamitron dispersed in a liquid phase containing a mineral oil in an amount of approx. 60% by weight, a surfactant or surfactant mixture containing ethoxylated alkyl phenol (having 3-9 ethylene oxide units) wherein the alkyl group contains 4-15, especially 6-12, carbon atoms, and / or ethoxylated dialkylphenol (containing 4-14 ethyl enoxide units) wherein the alkyl group contains 4-15, especially 6-12, carbon atoms, and optionally a phosphoric acid ester salt and / or an alkyl or aryl or alkylaryl sulfonic acid salt, the total amount of surfactant or surfactant mixture being 10-15 weight percent. The mineral oil may be, for example, solvent-refined mineral oil in an amount of approx. 50% by weight combined with aromatic free petroleum (boiling point 190-240 ° C) in an amount of approx. For example, the ethoxylated dinonyl phenol (containing 9 ethylene units) may be present in an amount of about 10%. For example, about 5%, the ethoxylated nonylphenol (containing 4 ethylene oxide units) may be present in an amount of about For example, the phosphoric acid ester (Berol ™ 724) monoethanolamine salt may be present in an amount of about 3%. 5%.

The amount of dispersed phemedipham should preferably be 25-35% of the composition, and the amount of dispersed metamitron should preferably be 15-35%, especially 20-30%, of the composition prior to mixing. Combined preparations can be prepared by mixing phenmedipham and metamitrone dispersions. The dispersions made in this way are easy to dilute with water. Both phenmedipham and metamitron are dispersed satisfactorily, and the oily phase forms sufficiently stable emulsions in the water. In these oil-detergent mixtures, the solubility of phenmedipham and metamitron 30 is approx. 0.2%. The compositions are preferably substantially water-free, which increases the chemical stability of the active substances.

The invention is further illustrated by Examples 4-7 below, and the preparation, isolation and stability in isophorone of the compounds prepared by the process of DK Application No. 2210/85 are illustrated by Examples 1-3: DK 168348 B1 14 EXAMPLE 1

Preparation of methyl (3- (3-tolyl-carbamoyl oxy) phenyl) carbamate 8.35 g (0.05 mol) of methyl N- (3-hydroxyphenyl) carbamate (prepared as described below) in 75 ml water was poured into a 150 ml beaker with stirrer and the mixture stirred. Over 3/4 hour, 6.65 g (0.05 mole) of 3-tolyl isocyanate was added by means of a separatory funnel without further adjusting the temperature. During the addition, the pH was maintained at 9.5 by simultaneous addition of 50% NaOH solution.

After addition of the 3-tolyl isocyanate, stirring was continued for 1 hour. Then the product, which was a very fine, suspended powder, was filtered and dried to give 14.0 g (93.3%) of the title product, mp 139-143 ° C.

HPLC analysis showed a purity of 94.1%, with the remaining 5.9% being methyl N- (3-hydroxyphenyl) carbamate and a by-product, N, N '-di-3-tolylurea.

Preparation of methyl N- (3-hydroxyphenyl) carbamate 10.9 g (0.10 mole) of 3-aminophenol in 100 ml of water was poured into a 20 250 µl beaker fitted with a stirrer, thermometer and pH electrode. The suspension was stirred and cooled to 10 ° C by external cooling.

Using a separating funnel, 9.45 g (0.10 mol) of chloro-formic acid methyl ester was added to the suspension over 1 hour with continued stirring and the temperature was maintained at 8-12 ° C. With the addition of the ester, the pH was adjusted to 5.3 by the simultaneous addition of a 50% NaOH solution.

After addition of the ester, stirring and pH adjustment were continued for 1/2 hour while the temperature was allowed to rise to room temperature. Then the pH was lowered to 1.9 with DK 168348 B1 15 4N HCl for 1/4 hour to dissolve unreacted 3-aminophenol in the form of the hydrochloride.

The product, which was a fine, suspended powder, was filtered, washed twice with 25 ml of ice water and dried to give 15.0 g (90%) of methyl N- (3-hydroxyphenyl) carbamate, m.p. 94-95 ° C. Titration of the hydroxy group with 0.5N NaOH showed a purity of 98%.

EXAMPLE 2

Solvent extraction of methyl (3- (3-tolylcarbamoyloxy) phenyl) carbamate 11 liter of a reaction mixture containing ca. 88 g of methyl (3- (3-tolylcarbamoyloxy) phenyl) carbamate was prepared as described in Example 1, but the powder was not filtered. Analysis of the resulting final product showed a purity of 94%.

The pH of the reaction mixture was adjusted to 2 by the addition of hydrochloric acid and 100 g of sodium chloride was dissolved in the slurry. 300 g of isophorone was added with stirring and stirring was continued until the solid dissolved.

The isophorone phase was separated and dried using sodium sulfate. The sodium sulfate was filtered off and 5.0 g of acetic anhydride was added.

Analysis showed a content of 21.6% methyl (3- (3-tolylcarbamoylloxy) phenyl) carbamate.

Example 16 Stability tests

A solution of methyl (3- (3-tolylcarbamoyloxy) phenyl) carbamate in isophorone was prepared as described in Example 25 and divided into 4 equal parts. The samples were subjected to storage tests as described in the table below, with or without the addition of acetic anhydride, optionally after drying with sodium sulfate. The tests were performed after 24 hours / 25 ° C, 26 days / 25 ° C and 25 days / 70 ° C, respectively.

Table

Active ingredient, percentage by weight Drying and / or stabilizing agent

15 agent added 24 hours / 25 ° C 26 days / 25 ° C 25 days / 70 ° C

20.68 20.93 20.56 1.0 g AAA / 50 ml 21.32 20.44 19.76

Na2 SO4 20.79 20.94 20.67 20 Na2 SO + 2 1.0 g AAA / 50 ml 21.56 20.43 19.69 AAA = Acetic anhydride.

EXAMPLE 4 Phenmedipham dispersions comprising an oil-based microemulsion or solution as the liquid phase

Microemulsions I and III and a solution II were prepared without phenmedipham by mixing the ingredients. Then, 1 part by weight of phenmedipham (technical purity, 96%) was incorporated into 3 parts by weight of the liquid phase II, II and III, and each of the resulting mixtures was ground in a ball mill filled with glass balls (diameter 1 mm).

DK 168348 B1 17

Turbidity temperatures of the microemulsions I and III and the solution II and the appearance of microemulsions formed therefrom after the addition of tap water are given in Table 1. It can be seen that they all appear as 5 homogeneous liquids which are not separated in their components.

After standing for 3 weeks at 45-50 ° C, all the phenme-dipham-containing dispersions were uniform after moderate shaking.

Table 1

I II III

Water 25.9% 21.0%

Monoethanolamine 2.6% Berol ™ 724 1) 10.3%

Triethanolamine 2.5% 2.0%

Sulfosoft ™ 2) 5.7% 4.5%

Spindle oil 5) 17.2% 28.4% 18.2%

Marlophen ™ 88H 3> 12.1% 18.5% 12.8% Berol ™ 2G 4> 5.2% 12.8% 8.2%

Butyl glycol 1.7% 7.1% 4.6%

Propylene glycol 3.7% Total 75.0% 75.0% 75.0% 25 Appearance translucent translucent yellow liquid yellowish brown liquid equal yellow liquid pH (in 1: 10 dilution with water) 2.8 3.4 3.7 Turbidity

temp. 60 ° C> 80 ° C 58 ° C

Dilution 1: 1 translucent translucent translucent yellow liquid yellow liquid equal yellow liquid

Dilution 1: 1, slightly cloudy translucent translucent liquid after 24 hours liquid gelatin

Dilution 1:10 translucent translucent translucent opaque fluid fluid fluid

Dilution 1:50 translucent opaque, but translucent liquid translucent lightly similar to light opaque 40 opaque liquid liquid

Phenmedipham, technical purity, 96% 25% 25% 25% DK 168348 Bl 18

Table 1 continued% phenmedipham in the preparation 24% 24% 24% 5 1)

Acid Phosphoric Acid Ester (Berol Chemistry) 2)

Dodecylbenzenesulfonic acid (Berol Chemistry) 3)

Ethoxylated nonylphenol (8 ethylene oxide units per molecule) (Huls) 4)

Ethoxylated nonylphenol (4 ethylene oxide units per molecule) 10 (Berol Chemistry) 5) Gravex ™ (Shell) EXAMPLE 5

Phenmedipham and metamitrone dispersion ions comprising an oil-based solution as the liquid phase 15 Dispersions I and II having the content set forth below were prepared in the same manner as described in Example 4.

Ingredients Dispersion I Dispersion II

Triethanolamine 2.6% 2.5%

Sulfosoft ™ 5.9% 5.7%

Spindle oil 29.3% 28.4%

Marlophen ™ 88H 19.1% 18.5%

Berol ™ 26 13.2% 12.8% 25 Butyl glycol 7.4% 7.1% 77.5% 75.0% DK 168348 B1 19

Ingredients Dispersion I Dispersion II

Metamitron, technical purity, 5 98% 22.5%

Phenmedipham, technical purity, 96% 25.0% pH of the dispersion 10 (in 1: 10 dilution with water) 3-4

A combined composition consisting of 75% by weight of dispersion I and 25% by weight of dispersion II was prepared by mixing the dispersions. The resulting composition was a viscous composition containing ca. 6% phenmedipham and approx. 17% metamitron, which could be diluted with water by some extended mixing and led to stable dispersions.

EXAMPLE 6

Metamitrone dispersion comprising an oil-based solution as the liquid phase

Solutions I and II were prepared by mixing and one part by weight of metamitron (technical purity, 98%) was incorporated into 3 parts by weight of the liquid phase in both I and II, and each of the resulting mixtures was ground in a ball mill. with glass balls (diameter 1 mm).

Turbidity temperatures for the resulting dispersions I and II and the appearance of the microemulsions formed by the addition of tap water to the dispersions are given in Table 2. It will be seen that they all appear as homogeneous liquids which are not separated. their components.

Table 2

5 I II

Monoethanolamine 2.9% 2.7%

724 12.6% 13.5%

Spindle oil 5) 33.6% 32.4% Solvesso ™ 1501 3.5% 3.4%

Marlophen ™ 88H 3) 14.0% 13.5%

Berol ™ 26 4) 8.4% 8.1% 60% solution of cocoalkyl-β-aminopropionic acid in diethyl glycol 0.0% 1.4% Total 75.0% 75.0%

Appearance translucent yellow liquid liquid 20 yellow liquid pH (in 1: 10 dilution with water) approx. 3 approx. 3

Turbiditetstemp. 45 ° C 44 ° C

25 Dilution 1: 1 translucent slightly cloudy yellow liquid liquid

Dilution 1:10 translucent opaque, but liquid through translucent 3 0 liquid dilution 1:50 translucent translucent translucent liquid

Technical purity, 35 metamitron, 98% 25% 25%

Solvesso ™ 150 is a 99% aromatic hydrocarbon, flash point 166 ° C, boiling point 187-210 ° C, from Exxon Corporation.

Example 16

Matamitron and phenmedipham dispersions comprising an oil-based solution as the liquid phase

Dispersions I and XI with the contents 5 listed in Table 3 were prepared in the same manner as described in Example 4.

Table 3

I II

10 -

Hydro Para 19 «51> 2 47.7

Halpasol "190/240 T> 10> 2 g, 5 26 * 3.1 2.9

Berol® 269 8) 5.1 4.8 15 Berol 724 h 4.4 4.1

Monoethanolamine 1.0 1.0 Total 75.0% 70.0%

Technical purity, 20 phenmedipham, 96% 30.0%

Technical purity, metamitron, 98% 25.0%% phenmedipham in the preparation 28.8%% metamitron in the composition 24.5% pH (in 1: 10 dilution with water) approx. 3 approx. 3 ^ Acid Phosphoric Acid Ester (Berol Chemistry) 4 4) Ethoxylated Nonylphenol (4 Ethylene Oxide Units Per Molecule) (Berol Chemistry) ® Solvent refined paraffinic mineral oil (Norsk Hydro) (4% aromatics, viscosity 19.7 cSt at 40 ° C) ^ Paraffinic hydrocarbon, < 0.1% aromatic hydrocarbon, boiling point 190-240 ° C, flash point> 70 ° C (Haltermann)

Claims (10)

8. Ethoxylated dinonylphenol (9 ethylene oxide units per mole kyle) (Berol Chemistry). In admixture with water, the oily preparations do not form stable transparent microemulsions as described in the above examples, but instead ordinary emulsions which, however, only precipitate very slowly. The tendency to excrete oil sediments containing fine-grained metamitron or phenmedipham is negligible. A combination composition of 77.5% by weight of dispersion I and 22.5% by weight of dispersion II was prepared by mixing the dispersions. The preparations contained approx. 19% metamitron and 6.5% phenmedipham. Dispersion I (metamitron) and the mixed dispersion 15 mentioned above are both thixotropic. Although somewhat viscous, they are easily mixed (emulsified and dispersed) in 98-95% water. The mixing is made easier as the density of the dispersions is less than the density of water. 20 PATENT REQUIREMENTS 1. Stabilized liquid herbicide composition containing phenmedipham and / or desmedipham characterized in that the composition is in the form of an emulsion containing phenmedipham and / or desmedipham dispersed in a liquid phase consisting mainly of mineral oil and / or vegetable oil, a surfactant component and optionally water, the composition comprising a) 5-40% by weight of phenmedipham and / or desme dipham having a particle size less than 10 microns. B) 15-65% by weight of one or more mineral oils and / or vegetable oils, c) 5-40% by weight of a surfactant containing one or more surfactants, and d) up to 40% by weight of water, and which composition is capable of forming a stable ready-to-use oil-in-water emulsion or micro-emulsion by mixing with water in a ratio of 1 part preparation to 1-10 parts of water. A liquid herbicide composition according to claim 1, characterized in that at least 50% of phenme-dipham and / or desmedipham have a particle size of less than 3-5 microns. A herbicide composition according to claim 1 or claim 2 containing water, characterized in that the liquid phase is acidic. A composition according to claim 3, 20, characterized in that the liquid phase has a pH of 2-4. A composition according to any one of claims 1-4, 2 characterized in that it further contains 5-amino-4-chloro-2-phenyl-3 (2H) -pyridazinone 3 (chloridazone). , 2-Ethoxy-2,3-dihydro-3,3-dimethylbenzofuran-5-yl-methanesulfonate (ethofumesate) or 4 4-amino-4,5-dihydro-3-methyl-6-phenyl-1,2 , 4-1riazine-5-one (metamitron). DK 168348 B1 24 Process for the preparation of a herbicide composition according to any one of claims 1-5, characterized in that phenmedipham and / or desmedipham are mixed with the other components of the composition and the mixture is subjected to grinding or fine grinding to disperse phenmedipham and / or desmedipham in the liquid phase. Process for the preparation of a herbicide preparation according to any one of claims 1-4, 10, characterized in that phenmedipham and / or desmedipham in the form of an aqueous slurry are comminuted such that phenmedipham and / or desmedipham have a particle size of less than 10 microns, after which the slurry is mixed with the other components to form an emulsion. A method for controlling weeds, characterized in that a herbicide composition according to any one of claims 1-5 is added to an area where weeds grow or are expected to grow. Method according to claim 8, characterized in that the herbicidal composition is used for the control of weeds in beets.